JP2012251131A - Molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material that has improved specific strength and specific modulus, and also has superior molding properties.SOLUTION: The molding material comprises a phenol resin, carbon fiber, and a polyethersulfone and/or a polyetherimide.

Description

  The present invention relates to a molding material and a scroll molded product.

  In recent years, attempts have been made to replace metal materials conventionally used in these molded products with resin materials from the viewpoint of reducing the weight of materials such as molded products and molded parts and reducing costs. In this attempt, various resins have been studied and used as materials for molded products and molded parts that have conventionally used metals. As such a resin material, a carbon / resin composite material including a phenol resin and carbon fiber has been proposed (for example, Patent Document 1).

  On the other hand, phenol resin molding materials excellent in heat resistance, dimensional stability, moldability and the like are used in key industry fields such as the automobile field, the electric field, and the electronic field. In particular, glass fiber reinforced phenolic resin is used as an alternative to metal part materials, and thus can be significantly reduced in cost, and therefore, active alternative studies have been conducted (for example, Patent Document 2).

  Among the automotive fields, glass fiber reinforced phenols are used in scroll compressors for automobiles in place of conventional metal materials in order to improve the fuel efficiency of automobiles. In detail, according to the life cycle assessment (LCA) of the scroll compressor for automobiles, the amount of carbon dioxide generation is much during the driving of the automobile. In order to reduce the amount of carbon dioxide generation, it is necessary to improve the fuel consumption. In order to reduce the amount of generation, it is necessary to improve the fuel consumption of automobiles. Therefore, studies have been made to replace metal parts used in scroll compressors for automobiles with resin parts to reduce the weight, and glass fiber reinforced phenolic resin is used as such a resin. (For example, patent document 3).

  However, the current glass fiber reinforced phenolic resin molding material may be insufficient for use as a scroll compressor molding material because it may lack strength and elastic modulus to be used as a scroll compressor material for automobiles. There is a need for a phenolic resin molding material having properties such as bending strength, flexural modulus, and toughness.

Japanese Patent No. 3915045 JP 2005-281364 A JP 2000-169669 A

  The present invention has been made in view of such circumstances, and provides a molding material having improved specific strength and specific elastic modulus and excellent molding characteristics. The present invention also provides, for example, a molding material having a specific strength and a specific elastic modulus sufficient to be used as a material for a scroll compressor for automobiles and having excellent molding characteristics.

  According to this invention which solves the said subject, the molding material containing a phenol resin, carbon fiber, and polyethersulfone and / or polyetherimide is provided.

  According to one embodiment of the present invention, in the molding material, the phenol resin is at least one selected from the group consisting of a novolac type phenol resin, a resol type phenol resin, and an aryl alkylene type phenol resin.

  According to one embodiment of the present invention, in the molding material, the carbon fiber is a pitch-based or PAN-based carbon fiber.

  According to one embodiment of the present invention, in the molding material, the polyethersulfone resin has a structure represented by the formula (1).

（式（１）中、ｎは１以上の整数である）

(In formula (1), n is an integer of 1 or more)

  According to one embodiment of the present invention, in the molding material, the polyetherimide resin has a structure represented by the formula (2).

（式（２）中、ｎは１以上の整数である）

(In formula (2), n is an integer of 1 or more)

  In one embodiment of the present invention, the phenol resin is in an amount of 25 wt% or more and 64 wt% or less based on the total weight of the molding material.

  According to one embodiment of the present invention, in the molding material, the carbon fiber is in an amount of 20 wt% or more and 60 wt% or less with respect to the total weight of the molding material.

  According to one embodiment of the present invention, in the molding material, the polyethersulfone is in an amount of 0.1 wt% or more and 20 wt% or less based on the total weight of the molding material.

  Moreover, according to this invention, the scroll molded article containing the molding material containing a phenol resin, carbon fiber, and polyethersulfone and / or polyetherimide is provided.

  According to one embodiment of the present invention, in the scroll molded article, the phenol resin is at least one selected from the group consisting of a novolac type phenol resin, a resol type phenol resin, and an aryl alkylene type phenol resin.

  According to one embodiment of the present invention, in the scroll molded article, the carbon fiber is a pitch-based or PAN-based carbon fiber.

  According to one embodiment of the present invention, in the scroll molded article, the polyethersulfone resin has a structure represented by the formula (1).

（式（１）中、ｎは１以上の整数である）

(In formula (1), n is an integer of 1 or more)

  According to one embodiment of the present invention, in the scroll molded article, the polyetherimide resin has a structure represented by Formula (2).

（式（２）中、ｎは１以上の整数である）

(In formula (2), n is an integer of 1 or more)

  According to one embodiment of the present invention, in the scroll molded article, the phenol resin is in an amount of 30.5 wt% or more and 55 wt% or less with respect to the total weight of the molding material.

  According to one embodiment of the present invention, in the scroll molded article, the carbon fiber is in an amount of 35 wt% or more and 55 wt% or less with respect to the total weight of the molding material.

  According to an embodiment of the present invention, in the scroll molded article, the polyethersulfone is in an amount of 0.5 wt% or more and 15 wt% or less with respect to the total weight of the molding material.

  According to the present invention, there are provided a molding material having an improved specific strength and a specific elastic modulus and having excellent molding characteristics, and a scroll molded product including such a molding material.

  The molding material according to the invention comprises a phenolic resin, carbon fibers and polyethersulfone or polyetherimide.

  Examples of the phenol resin used in the present invention include novolac type phenol resins, resol type phenol resins, aryl alkylene type phenol resins and the like.

  The novolak-type phenol resin used in the present invention can be obtained, for example, by reacting phenols and aldehydes under an acidic catalyst.

  Examples of the phenols used in the production of the novolak type phenol resin include phenol, cresol, xylenol, ethylphenol, p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, p-octylphenol, and p-nonylphenol. , P-cumylphenol, bisphenol A, bisphenol F, resorcinol and the like. These can be used alone or in combination of two or more.

  Examples of the aldehydes used for producing the novolak type phenol resin include alkyl aldehydes such as formaldehyde, acetaldehyde, propyl aldehyde and butyraldehyde, and aromatic aldehydes such as benzaldehyde and salicylaldehyde. Examples of the formaldehyde source include formalin (aqueous solution), paraformaldehyde, hemi-formal with alcohols, and trioxane. These can be used alone or in combination of two or more.

  In the synthesis of the novolak type phenol resin, the reaction molar ratio of phenols and aldehydes is usually 0.3 to 1.0 mol, particularly 0.6 to 0, with respect to 1 mol of phenol. .9 mol is preferable.

  Examples of the acidic catalyst include organic carboxylic acids such as oxalic acid and acetic acid, organic sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid and methanesulfonic acid, 1-hydroxyethylidene-1,1′-diphosphonic acid, 2- Examples thereof include organic phosphonic acids such as phosphonobutane-1,2,4-tricarboxylic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. In addition, these acidic catalysts can also be used individually or in combination of 2 or more types.

  The resol type phenol resin used in the present invention is obtained by reacting phenols with aldehydes.

  Examples of the phenols used in the production of the resol-type phenol resin of the present invention include cresols such as phenol, o-cresol, m-cresol, and p-cresol, 2,3-xylenol, 2,4-xylenol, 2, 5-xylenol, 2,6-xylenol, 3,4-xylenol, xylenols such as 3,5-xylenol, ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol, isopropylphenol, butylphenol , Butylphenols such as p-tert-butylphenol, p-tert-amylphenol, p-octylphenol, p-nonylphenol, alkylphenols such as p-cumylphenol, fluorophenol, chlorophenol, bromophenol, Halogenated phenols such as phenphenol, monovalent phenol substitutes such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol and trinitrophenol, and monovalent phenols such as 1-naphthol and 2-naphthol, Examples thereof include polyphenols such as resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, and dihydroxynaphthalene. These can be used alone or in admixture of two or more. Among these phenols, those selected from economically advantageous phenols, cresols, and bisphenol A are preferable.

  Examples of the aldehydes used in the production of the resol type phenolic resin of the present invention include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, carbaldehyde. Examples include proaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. These can be used alone or in combination of two or more. Among these aldehydes, preferred are those selected from formaldehyde and paraformaldehyde, which are excellent in reactivity and inexpensive.

  Examples of the synthesis method of the resol type phenol resin used in the present invention include a method in which the above-described phenols and aldehydes are reacted in the presence of a catalyst such as an alkali metal, an amine, or a divalent metal salt.

  Examples of the catalyst used when synthesizing the resol type phenol resin used in the present invention include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, and alkaline earth metals such as calcium, magnesium and barium. And amines such as sodium carbonate, aqueous ammonia, triethylamine and hexamethylenetetramine, and divalent metal salts such as magnesium acetate and zinc acetate. These can be used alone or in combination of two or more.

  In the synthesis of the resol type phenol resin, the reaction molar ratio between the phenol and the aldehyde is preferably 0.80 to 2.50 mol with respect to 1 mol of the phenol. More preferably, it is 1.00-2.30 mol of aldehydes. If the molar ratio is less than the lower limit, a resol-type resin may not be obtained, and if the molar ratio exceeds the upper limit, reaction control may be difficult.

  The aryl alkylene type phenol resin used in the present invention refers to an epoxy resin having one or more aryl alkylene groups in a repeating unit. Examples of such aryl alkylene type phenol resins include xylylene type epoxy resins and biphenyl dimethylene type epoxy resins. Among these, a biphenyl dimethylene type epoxy resin is preferable.

  The carbon fibers used in the present invention are pitch-based carbon fibers or PAN-based carbon fibers. These carbon fibers may be used alone or in combination of two or more. The shape of the carbon fiber used is not particularly limited, but a circular shape is preferable from the viewpoint of strength. The fiber diameter of the carbon fiber to be used is preferably 5 μm or more and 13 μm or less, more preferably 6 μm or more and 10 μm or less.

  As the polyether sulfone used in the present invention, commercially available products can be used. The polyethersulfone preferably contains a repeating unit represented by the following formula (1).

式（１）中、ｎは１以上の整数である。好ましくは、ｎは、１以上５００以下であり、より好ましくは１００以上３００以下である。

In formula (1), n is an integer of 1 or more. Preferably, n is 1 or more and 500 or less, more preferably 100 or more and 300 or less.

  As a polyetherimide used by this invention, what is generally used in the said field | area which has a structure represented by the following formula | equation (2) can be used.

（式（２）中、ｎは１以上の整数である）。

(In formula (2), n is an integer of 1 or more).

  Any of polyethersulfone and polyetherimide may be used alone or in combination.

  The weight of the phenol resin with respect to the total weight of the molding material is preferably 25% by weight to 64% by weight, more preferably 30% by weight to 60% by weight, and further preferably 35% by weight to 50% by weight. . If the upper limit is exceeded, blistering may occur in the resulting molded product, and if it is less than the lower limit, it may take time to cure and curing may be insufficient. Further, by setting the weight of the phenol resin to 30.5 wt% or more and 55 wt% or less with respect to the total weight of the molding material, it is possible to obtain a specific strength and a specific elastic modulus sufficient for use as a scroll.

  The weight of the carbon fiber with respect to the total weight of the molding material is preferably 20% by weight to 60% by weight, and more preferably 40% by weight to 55% by weight. When the above upper limit is exceeded, the surface state of the obtained molded product may be deteriorated, and the moldability and fluidity may be deteriorated. Moreover, when it is less than the said lower limit, mechanical characteristics, such as the intensity | strength of a molded product and an elasticity modulus, which are obtained may not be excellent. Moreover, when using the said molding material as a scroll molded article, it is preferable that the weight of the carbon fiber with respect to the total weight of a molding material is 35 to 55 weight%. Within the above range, it is possible to obtain a specific strength and a specific elastic modulus sufficient for use as a scroll.

  When using polyethersulfone, the weight of polyethersulfone is preferably 0.1% by weight or more and 20% by weight or less, more preferably 2% by weight or more and 8% by weight or less, based on the total weight of the molding material. By being within the above range, the obtained molded article can have excellent specific strength and specific elastic modulus. Moreover, when using the said molding material as a scroll molded article, it is preferable that the weight of polyethersulfone with respect to the total weight of a molding material is 0.5 to 15 weight%. Within the above range, it is possible to obtain a specific strength and a specific elastic modulus sufficient for use as a scroll.

  The molding material of the present invention may further contain components such as a mold release agent, a lubricant, a curing aid, a pigment, an inorganic filler, an elastomer, and glass fiber as necessary.

  Examples of inorganic fillers include silicates such as talc, fired clay, unfired clay, mica, oxides such as titanium oxide, alumina, silica, and fused silica, and carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite. Salts, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate And borate salts such as sodium borate, nitrides such as aluminum nitride, boron nitride, and silicon nitride, and glass fibers. Among these, glass fiber is preferable. When glass fiber is used, the mechanical strength of the obtained molded product can be maintained.

  Although the glass which comprises glass fiber is not specifically limited, For example, E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass etc. are mentioned. Among these, E glass, T glass, or S glass is preferable. Thereby, the high elasticity of glass fiber can be achieved and a thermal expansion coefficient can also be made small.

  Examples of the elastomer include acrylic acid-alkyl styrene copolymer, polyvinyl acetate, styrene-isoprene copolymer, acrylonitrile-budadiene copolymer, isoprene rubber, styrene-butadiene copolymer, ether-urethane copolymer, Examples thereof include a methyl-urethane copolymer, an ester-urethane copolymer, a vinyl-silicone copolymer, a phenyl-silicone copolymer, and a chloroprene copolymer. In particular, an acrylic acid-alkylstyrene copolymer, an acrylonitrile-budadiene copolymer, and the like have a wide application range and are easy to handle. Therefore, it is preferable to use these.

  The method for producing the molding material of the present invention is not particularly limited, but it is produced by mixing the above components and crushing the kneaded material heated and kneaded with a pressure kneader, a twin screw extruder, a heating roll, etc., with a power mill or the like. . The molding material thus obtained can be applied to injection molding, transfer molding, compression molding and the like to obtain a molded product having a desired shape.

  Hereinafter, the present invention will be described by way of examples.

Example 1

  Novolak type phenolic resin, 43.3% by weight, carbon fiber, 46.5% by weight, polyethersulfone, 0.1% by weight, hexamethylenetetramine as a curing agent, 7.1% by weight, based on the whole molding material A raw material mixture containing 1% by weight of magnesium oxide, 1% by weight of a release agent and 1% by weight of a coloring agent as a curing aid is melt-kneaded for 3 minutes with a heating roll at 90 ° C., taken out, pulverized, and pulverized into granules. Thus, a molding material was obtained.

  The tensile strength, tensile elastic modulus, and loss factor of the molded product obtained by injection molding were measured by the method described in “Evaluation Method” below. The results are shown in Table 1.

(Evaluation method)
Test pieces were prepared by injection molding using the molding materials obtained in the examples and comparative examples. The molding conditions were a mold temperature of 175 ° C. and a curing time of 1 minute.

  The obtained test piece was treated in an atmosphere at 180 ° C. for 6 hours, and the tensile strength (room temperature), tensile elastic modulus (room temperature) and loss factor (room temperature) were set in JIS K 6911 “General Thermosetting Plastic Testing Method”. Measured in conformity.

  In addition, as an evaluation result of the scroll molded product in Table 1, “◎” is suitable for scrolling, “○” is suitable for general-purpose products, and “×” is not suitable for either. Has been.

(Examples 2-23, Comparative Examples 1-2)

  Using the components shown in Table 1, a molding material was obtained by using the same method as in Example 1. The amounts of the components shown in Table 1 are all weight percent. In addition, the component of Table 1 used the following.

(1) Phenol resin (novolak type phenol resin): PR-HF-3 manufactured by Sumitomo Bakelite
(2) Carbon fiber (PAN type): HT C261 6 mm manufactured by Toho Tenax Co., Ltd.
(3) Carbon fiber (pitch type): DIALEAD K223SE manufactured by Mitsubishi Plastics
(4) Glass fiber: E glass fiber manufactured by Nitto Boseki Co., Ltd. (5) PES-1 (polyethersulfone): Sumitomo Chemical Co., Ltd. 5003PS
(6) PES-2 (polyether sulfone): Sumitomo Chemical 4800P
(7) PEI-1 (polyetherimide): Ultem1000 manufactured by SABIC Innovative Plastics
(8) PEI-2 (polyetherimide): Ultem 1040A manufactured by SABIC Innovative Plastics
(9) Curing agent (hexamethylenetetramine): Sumitomo Seika Co., Ltd. Urotropin (10) Curing aid: Magnesium oxide (11) Release agent: Calcium stearate (12) Colorant: Carbon black The results are summarized in the following table. Show.

The present invention relates to molding materials.

According to the present invention, which has improved specific strength and specific elastic modulus, and provides a molded materials having excellent molding characteristics.

Claims (16)

Phenolic resin,
Carbon fiber,
Polyethersulfone and / or polyetherimide,
Including molding materials.   2. The molding material according to claim 1, wherein the phenol resin is at least one selected from the group consisting of a novolac-type phenol resin, a resol-type phenol resin, and an arylalkylene-type phenol resin.   The molding material according to claim 1, wherein the carbon fibers are pitch-based or PAN-based carbon fibers. The molding material according to claim 1, wherein the polyethersulfone has a structure represented by the formula (1).

(In formula (1), n is an integer of 1 or more) The molding material of Claim 1 in which the said polyetherimide has a structure shown by Formula (2).

(In formula (2), n is an integer of 1 or more)   The molding material according to claim 1, wherein the phenolic resin is in an amount of 25 wt% or more and 64 wt% based on the total weight of the molding material.   The molding material according to claim 1, wherein the carbon fiber is in an amount of 20% by weight or more and 60% by weight or less based on the total weight of the molding material.   The molding material according to claim 1, wherein the polyethersulfone is in an amount of 0.1 wt% or more and 20 wt% or less with respect to the total weight of the molding material. Phenolic resin,
Carbon fiber,
A scroll molded article comprising a molding material containing polyethersulfone and / or polyetherimide.   The scroll molded article according to claim 9, wherein the phenol resin is at least one selected from the group consisting of a novolac type phenol resin, a resol type phenol resin, and an aryl alkylene type phenol resin.   The scroll molded product according to claim 9, wherein the carbon fibers are pitch-based or PAN-based carbon fibers. The scroll molded article according to claim 9, wherein the polyethersulfone has a structure represented by the formula (1).

(In formula (1), n is an integer of 1 or more) The scroll molded article according to claim 9, wherein the polyetherimide has a structure represented by the formula (2).

(In formula (2), n is an integer of 1 or more)   The scroll molded product according to claim 9, wherein the phenolic resin is in an amount of 30.5 wt% or more and 55 wt% or less with respect to the total weight of the molding material.   The scroll molded product according to claim 9, wherein the carbon fiber is in an amount of 35 wt% or more and 55 wt% or less with respect to the total weight of the molding material.   The scroll molded product according to claim 9, wherein the polyethersulfone is in an amount of 0.5 wt% or more and 15 wt% or less with respect to the total weight of the molding material.